Nonrelativistic protocol for calculating the 1J(195Pt-15N) coupling constant in Pt(II)-complexes using all-electron Gaussian basis-set

195Pt and 15N NMR Data in Square Planar Platinum(II) Complexes of the Type [Pt(NH3)aXb]n (Xb = Combination of Halides): “NMR Effective Molecular Radius” of Coordinated Ammonia

“…The problem of fully understanding the phenomena influencing the δ NMR signals frequencies, related to the physical properties of a molecule, deserved a particular attention in the recent literature , . In this context, ab initio quantitative theoretical calculations often resulted in a better understanding of the mechanisms determining the observed NMR chemical shifts , .…”

Predicting Pt-195 NMR Chemical Shift and 1J(195Pt-31P) Coupling Constant for Pt(0) Complexes Using the NMR-DKH Basis Sets

“…As shown in our previous papers [18][19][20], the inclusion of relativistic effects is fundamental for the theoretical prediction of NMR parameters of the heavy Pt-195 nucleus. Relativistic Hamiltonians are not always available in computational packages, so the construction of nonrelativistic computational protocols must be of great interest and useful if properly scaled.…”

“…The Pt-195 NMR shielding constant (σ 195 Pt) and the 1 J( 195 Pt-31 P) were calculated from the gauge-independent atomic orbitals (GIAO) [35,36] method at DFT level using the GGA PBE [37] functional with the NMR-DKH [18] basis sets (GIAO-PBE/NMR-DKH/IEF-PCM(UFF)). The computational protocol (NMR/geometry) is represented as in our previous papers [18,19], namely, GIAO-PBE/NMR-DKH/IEF-PCM(UFF)//B3LYP/LANL2DZ/ def2-SVP/IEF-PCM(UFF). All calculations were carried out in the GAUSSIAN 09 program Revision D.01 [38].…”

“…Theoretical prediction of Pt-195 NMR parameters is a difficult task, as several factors must be taken into account, such as the geometry of the complexes, electronic correlation, basis sets, solvents, and relativistic effects [16][17][18][19][20]. Despite this difficulty, some works on the theoretical prediction of δ 195 Pt and 1 J 195 Pt-L for Pt(II) and Pt(IV) complexes can be found in the literature [18][19][20][21][22][23][24][25][26]. However, computational studies on NMR prediction of Pt-195 in Pt(0) complexes are still very scarce [27].…”

“…Then, the same computational protocol as in Ref. [18] was used to build an empirical model for predicting 1 J( 195 Pt-15 N) for a set of 71 Pt(II) complexes, which yielded a MAD of 36 Hz and an MRD of 10.4% [19]. In the present work, we extend our previous studies by proposing quantum mechanical computational schemes to predict Pt-195 NMR chemical shift and 1 J( 195 Pt-31 P) for Pt(0) complexes.…”